FAMn:PbI3 perovskite films were synthesized and probed mainly through
electron spin resonance (ESR) spectroscopy. FAMn:PbI3 with low (~1%)
Mn concentration showed a hyperfine sextet line originated from Mn++ ions. FAMn:PbI3 with high (10%) Mn concentration showed broad
resonance (~500 G peak-to-peak linewidth).
However, after bombardment of FAMn:PbI3with high Mn
concentration by focused ion beams (FIB), a sharp ESR peak appeared. The
peak-to-peak linewidth (ΔHpp) was ~8 G regardless of the
temperature. The FIB-induced defect showed Curie behavior at low temperatures (5 K -
50 K), which indicates the presence of localized electrons at the defect sites
at low temperatures. The g-value increased from g = 2.0002 to 2.0016 as the
temperature increased from 5 K to 50 K. Together with the ongoing search for
electron spin echo (ESE), this could potentially provide a platform for realizing
magnetic bits, information storage, and increased manipulation speed.
References
[1]
Jeon, N.J., Noh, J.H., Yang, W.S., Kim, Y.C., Ryu, S., Seo, J. and Seok, S.I. (2015) Compositional Engineering of Perovskite Materials for High-Performance Solar Cells. Nature, 517, 476-480. https://doi.org/10.1038/nature14133
[2]
Yang, W.S., Noh, J.H., Nam, J.J., Kim, Y.C., Ryu, S., Seo, J. and Seok, S.I. (2015) High-Performance Photovoltaic Perovskite Layers Fabricated through Intramolecular Exchange. Science, 348, 1234-1237. https://doi.org/10.1126/science.aaa9272
[3]
Han, Q., Bae, S.-H., Sun, P., Hsieh, Y.-T., Yang, Y., Rim, Y.S., Zhao, H., Chen, Q., Shi, W., Li, G. and Yang, Y. (2016) Single Crystal Formamidinium Lead Iodide (FAPbI3): Insight into the Structural, Optical, and Electrical Properties. Advanced Materials, 28, 2253-2258. https://doi.org/10.1002/adma.201505002
[4]
Chen, Z., Zhang, H., Yao, F., Tao, C., Fang, G. and Li, G. (2020) Room Temperature Formation of Semiconductor Grade α-FAPbI3 Films for Efficient Perovskite Solar Cells. Cell Reports Physical Science, 1, Article ID: 100205. https://doi.org/10.1016/j.xcrp.2020.100205
[5]
Tan, S., Yavuz, I., Weber, M.H., Huang, T., Chen, C.-H., Wang, R., Wang, H.-C., Ko, J.H., Nuryyeva, S., Xue, J., Zhao, Y., Wei, K.-H., Lee, J.-W. and Yang, Y. (2020) Shallow Iodine Defects Accelerate the Degradation of α-Phase Formamidinium Perovskite. Joule, 4, 2426-2442. https://doi.org/10.1016/j.joule.2020.08.016
[6]
Xia, W., Pei, Z., Leng, K. and Zhu, X. (2020) Research Progress in Rare Earth-Doped Perovskite Manganite Oxide Nanostructures. Nanoscale Research Letters, 15, Article No. 9. https://doi.org/10.1186/s11671-019-3243-0
[7]
Náfrádi, B., Szirmai, P., Spina, M., Lee, H., Yazyev, O.V., Arakcheeva, A., Chernyshow, D., Gibert, M., Forró, L. and Horváth, E. (2016) Optically Switched Magnetism in Photovoltaic Perovskite CH3NH3(Mn:Pb)I3. Nature Communications, 7, Article No. 13406. https://doi.org/10.1038/ncomms13406
[8]
Achermann, M., Hollingsworth, J.A. and Klimov, V.I. (2003) Multiexcitons Confined within a Subexcitonic Volume: Spectroscopic and Dynamical Signatures of Neutral and Charged Biexcitons in Ultrasmall Semiconductor Nanocrystals. Physical Review B, 68, Article ID: 245302. https://doi.org/10.1103/PhysRevB.68.245302
[9]
Dey, A. and Yarlagadda, S. (2018) Temperature Dependence of Long Coherence Times of Oxide Charge Qubits. Scientific Reports, 8, Article No. 3487. https://doi.org/10.1038/s41598-018-21767-2
[10]
Jeon, N.J., Yang, T.-Y., Park, H.H., Seo, J., Nam, D.Y., Jeong, D., Hong, S., Kim, S.H., Cho, J.M., Jang, J.J. and Lee, J.-K. (2019) Thermally Activated, Light-Induced Electron-Spin-Resonance Spin Density Reflected by Photocurrents in a Perovskite Solar Cell. Applied Physics Letters, 114, Article ID: 013903. https://doi.org/10.1063/1.5053830
[11]
Qiao, L., Sun, X. and Long, R. (2019) Mixed Cs and FA Cations Slow Electron-Hole Recombination in FAPbI3 Perovskites by Time-Domain ab Initio Study: Lattice Contraction versus Octahedral Tilting. The Journal of Physical Chemistry Letters, 10, 672-678. https://doi.org/10.1021/acs.jpclett.8b03729
[12]
Palei, M., Motapothula, M., Ray, A., Abdelhady, A.L., Lanzano, L., Prato, M., Panda, J.K., et al. (2020) Photoluminescence Enhancement and High Accuracy Patterning of Lead Halide Perovskite Single Crystals by MeV Ion Beam Irradiation. Journal of Materials Chemistry C, 8, 9923-9930. https://doi.org/10.1039/D0TC02326D
[13]
D’Innocenzo, V., Grancini, G., Alcocer, M.J.P., Kandada, A.R.S., Stranks, S.D., Lee, M.M., Lanzani, G., Snaith, H.J. and Petrozza, A. (2014) Excitons versus Free Charges in Organo-Lead Tri-Halide Perovskites. Nature Communications, 5, Article No. 3586. https://doi.org/10.1038/ncomms4586
[14]
Saba, M., Cadelano, M., Marongiu, D., Chen, F., Sarritzu, V., Sestu, N., Figus, C., Aresti, M., Piras, R., Lehmann, A.G., Cannas, C., Musinu, A., Quochi, F., Mura, A. and Bongiovanni, G. (2014) Correlated Electron-Hole Plasma in Organometal Perovskites. Nature Communications, 5, Article No. 5049. https://doi.org/10.1038/ncomms6049
[15]
Sestu, N., Cadelano, M., Sarritzu, V., Chen, F., Marongiu, D., Piras, R., Mainas, M., Quochi, F., Saba, M., Mura, A. and Bongiovanni, G. (2015) Absorption F-Sum Rule for the Exciton Binding Energy in Methylammonium Lead Halide Perovskites. The Journal of Physical Chemistry Letters, 6, 4566-4572. https://doi.org/10.1021/acs.jpclett.5b02099
[16]
Yang, Y., Yang, M., Li, Z., Crisp, R., Zhu, K. and Beard, M.C. (2015) Comparison of Recombination Dynamics in CH3NH3PbBr3 and CH3NH3PbBr3 Perovskite Films: Influence of Exciton Binding Energy. The Journal of Physical Chemistry Letters, 6, 4688-4692. https://doi.org/10.1021/acs.jpclett.5b02290
[17]
Yang, Y., Yan, Y., Yang, M.J., Choi, S., Zhu, K., Luther, J.M. and Beard, M.C. (2015) Low Surface Recombination Velocity in Solution-Grown CH3NH3PbBr3 Perovskite Single Crystal. Nature Communications, 6, Article No. 7961. https://doi.org/10.1038/ncomms8961
[18]
Yang, Y., Yang, M., Zhu, K., Johnson, J.C., Berry, J.J., van de Lagemaat, J. and Beard, M.C. (2016) Large Polarization-Dependent Exciton Optical Stark Effect in Lead Iodide Perovskites. Nature Communications, 7, Article No. 12613. https://doi.org/10.1038/ncomms12613
[19]
Jakes, P. and Erdem, E. (2011) Finite Size Effects in ZnO Nanoparticles: An Electron Paramagnetic Resonance (EPR) Analysis. Physica Status Solidi—Rapid Research Letters, 5, 56-58. https://doi.org/10.1002/pssr.201004450
[20]
Cho, J.M., Seo, J.M., Lee, J.-K., Zhang, H. and Lamb, R. (2009) Electronic Properties of Oxygen Vacancies in Titania Nanotubes. Physica B: Condensed Matter, 404, 127-130.
https://doi.org/10.1016/j.physb.2008.10.027
